US20220316041A1 - Manufacturing Method for Tubular Products made of Zirconium-Based Alloy - Google Patents
Manufacturing Method for Tubular Products made of Zirconium-Based Alloy Download PDFInfo
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- US20220316041A1 US20220316041A1 US17/257,283 US201917257283A US2022316041A1 US 20220316041 A1 US20220316041 A1 US 20220316041A1 US 201917257283 A US201917257283 A US 201917257283A US 2022316041 A1 US2022316041 A1 US 2022316041A1
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- thermal treatment
- tubular products
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 14
- 239000000956 alloy Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000007669 thermal treatment Methods 0.000 claims abstract description 35
- 238000005097 cold rolling Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000007731 hot pressing Methods 0.000 claims abstract description 14
- 239000011253 protective coating Substances 0.000 claims abstract description 10
- 238000010791 quenching Methods 0.000 claims abstract description 10
- 230000000171 quenching effect Effects 0.000 claims abstract description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005242 forging Methods 0.000 claims abstract description 9
- 238000005496 tempering Methods 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 7
- 230000008018 melting Effects 0.000 claims abstract description 7
- 238000010313 vacuum arc remelting Methods 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 238000005553 drilling Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 abstract description 15
- 230000007797 corrosion Effects 0.000 abstract description 15
- 230000008569 process Effects 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 229910001093 Zr alloy Inorganic materials 0.000 description 11
- 239000011651 chromium Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000000137 annealing Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000003746 surface roughness Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 238000005275 alloying Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 238000005098 hot rolling Methods 0.000 description 5
- 239000010955 niobium Substances 0.000 description 5
- 238000001953 recrystallisation Methods 0.000 description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000009740 moulding (composite fabrication) Methods 0.000 description 4
- 229910052758 niobium Inorganic materials 0.000 description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 102220253765 rs141230910 Human genes 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001192 hot extrusion Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910020900 Sn-Fe Inorganic materials 0.000 description 1
- 229910019314 Sn—Fe Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 102200052313 rs9282831 Human genes 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 238000009966 trimming Methods 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/10—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of tubular bodies
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C16/00—Alloys based on zirconium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B37/00—Control devices or methods specially adapted for metal-rolling mills or the work produced thereby
- B21B37/78—Control of tube rolling
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/08—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/08—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for tubular bodies or pipes
- C21D9/085—Cooling or quenching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/008—Using a protective surface layer
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/02—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working in inert or controlled atmosphere or vacuum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/186—High-melting or refractory metals or alloys based thereon of zirconium or alloys based thereon
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E30/00—Energy generation of nuclear origin
- Y02E30/30—Nuclear fission reactors
Definitions
- the invention is referred to the nuclear technical field, particularly to production of zirconium alloy tubular products used as the structural components of the core in water-cooled nuclear reactors, including the reactors of VVER and PWR type.
- Zirconium alloys are used as the materials for structural components of power nuclear reactors due to their unique properties: small thermal absorption section as well as physical and mechanical properties.
- the requirements for corrosion resistance and hydrogen absorption in high-temperature water and water steam, strength, irradiation growth, thermal and thermal-radiation creep are imposed on the zirconium alloy products for the reactor core.
- the materials shall also have high processibility characteristics. Properties and processibility of the products made of this alloy depend not only on the composition but also on their manufacturing method including the ingot melting, hot and cold processing, thermal treatment regimes for the intermediate and final size, as well as the final finishing operations.
- the patent “Tubes Made of Zirconium-Based Alloys and Their Manufacturing Method” RU 2298042C2 (published on 27 Apr. 2004, cl. C22F/1/18C21D1/18, C22C16/00) is known.
- the manufacturing method includes homogenizing processing of the extruded hollow billets, their quenching with water, stress relieving, double-stage cold rolling with intermediate and final annealing.
- the drawbacks of this patent reside in the fact that no protective coating is applied prior to hot extrusion resulting in oxidation of the metal in the course of the process and reduction of the processibility of tubular products.
- Application of the double-rolling cold processing scheme with final homogenizing processing in the ( ⁇ + ⁇ )-area enables to achieve high strength of the product, in this case annealing in the ( ⁇ + ⁇ )-area results in generation of the metastable ⁇ -Zr-phase in the product structure affecting corrosion of zirconium alloys.
- the process flow diagram does not provide for any final finishing operations enabling to remove residual process contaminations from the surface of tubular products and reduce the surface roughness thus decreasing corrosion resistance of the products.
- the patent specifies the composition of corrosion-resistant zirconium alloy and the method for manufacturing of fuel element claddings made of this alloy, including the ingot melting, the ingot coating with the protective steel shell, thermal treatment of the ingot together with the shell prior to hot rolling, hot rolling, removal of the protective steel coating, thermal treatment of hot-rolled tubular billets, three runs of cold rolling, intermediate thermal treatment after each rolling and final thermal treatment.
- the process flow diagram does not provide for any final finishing operations enabling to remove residual process contaminations from the surface of tubular products and reduce the surface roughness thus decreasing corrosion resistance of the products.
- the purpose of this invention is to develop the manufacturing method for the tubular products used as the structural components of the core in water-cooled nuclear reactors, including the reactors of VVER and PWR type.
- the technical result is processibility of the material at all stages of hot and cold pressure shaping applied in the course of tubular product manufacturing as well as high strength characteristics and corrosion resistance of the tubular products.
- Multi-stage hot forging of the ingot is carried out at the temperature of 980° C. to 720° C. with the total deformation degree of up to 93% and with intermediate heating at the temperature of 890° C. to 850° C.
- Tubular billets are produced by drilling of the axial center hole and subsequent boring of the axial center hole in the round-profile blank divided into cut-to-length sections.
- Quenching is carried out at the temperature of 1050-1100° C. and tempering at the temperature of 450-600° C.
- Vacuum thermal treatment of the tubular billets in the intervals between hot pressing and cold rolling is carried out at the temperature of 605-630° C.
- Vacuum thermal treatment of the tubular billets in the intervals between cold rollings is carried out at the temperature of 570-630° C.
- the final vacuum thermal treatment of the tubular products is carried out at the temperature of 535-545° C.
- the final vacuum thermal treatment of the tubular products is carried out at the temperature of 600-620° C.
- Vacuum thermal treatment of the tubular products is carried out at the residual pressure in the furnace not exceeding 1 ⁇ 10 ⁇ 4 -1 ⁇ 10 ⁇ 5 mm Hg.
- the selected proportion of alloying components in the zirconium alloy provides for the processing properties, corrosion resistance, stable characteristics of mechanical properties and deformation resistance of the tubular products.
- the advantage of the tubular product manufacturing in accordance with the claimed method resides in the fact that hot thermo-mechanical treatment ensures uniform processing of the cast structure along the ingot length and cross-section, and application of the protective coating provides for protection against gas pickup and prevents diffusion interaction between the coating and the tubular billet.
- the process also provides for manufacturing of the tubular products with the maximum possible fracture viscosity and ductility level for this composition.
- the final vacuum thermal treatment of the tubular products is carried out in two different temperature ranges.
- the first range (535-545° C.) provides for formation of the homogeneous partially recrystallized structure (the recrystallization degree of at least 40%), and the second range (600-620° C.) provides for formation of the homogeneous recrystallized structure (the recrystallization degree of 100%).
- Final finishing operations provide for the surface roughness Ra of less than 0.8 ⁇ m on the outer and inner surface thus increasing stability of the corrosion properties for the products.
- the method is embodied in the following way:
- the manufacturing technology for zirconium tubular products includes the following operations. Melting of the alloy ingot consisting of: niobium 1.05-1.07% (wt.), stannum 1.24-1.27% (wt.), iron 0.31-0.34% (wt.), chromium 0.0025-0.003% (wt.), carbon 0.011-0.019% (wt.), oxygen 0.064-0.065% (wt.), silicon 0.0025-0.0035% (wt.), zirconium—all the rest.
- the initial alloying components are mixed with electrolytic zirconium powder, and then consumable electrodes are formed and melted by two-stage vacuum arc remelting. The side surface of the ingot is processed mechanically.
- the ingot is heated to the temperature of 980° C.
- Multi-stage hot forging of the ingot at the first stage is carried out at the temperature of 980° C., at the last stage—at the temperature of 720° C., with intermediate heating within the temperature range of 890° C. to 850° C.
- the total deformation ⁇ ⁇ for hot forging of the ingot is 93%. Heating and intermediate heat-up of the ingot is carried out in the electric resistance-type furnace. Round-profile blanks ⁇ 109 ⁇ 28.5 mm are manufactured by mechanical processing of the forged pieces.
- Tubular billets are produced by drilling of the axial center hole and subsequent boring of the axial center hole in the round-profile blank divided into cut-to-length sections.
- Quenching is carried out at the temperature of 1050-1100° C., and tempering—at the temperature of 450-600° C.
- the coating is applied on the tubular billets in order to protect them against gas pickup in the course of subsequent heating and hot pressing processes (for example, copper through the use of the copper coating application operation).
- Heating of the tubular billets for hot pressing is carried out in the electric resistance-type furnace.
- the tubular billets are rolled on the cold reducing mills of HPT, HPTR, KPW type in 5 runs with the total deformation ⁇ ⁇ of 41.8 to 56.5% per a run; in this case the tubular coefficient Q is within the range of 1.00-1.6, and the tubular products of uniform cross-section are produced.
- Intermediate vacuum thermal treatment is carried out within the temperature range of 570° C. to 610° C.
- Vacuum furnaces with the underpressure level of at least 1 ⁇ 10 ⁇ 4 -1 ⁇ 10 ⁇ 5 mm Hg are used.
- the tubes are subjected to a set of operations subsequent to the final annealing and trimming, particularly: jet etching, alkali treatment, grinding of the surface.
- the alloy tubular products ⁇ 12.60 ⁇ 11.24 mm manufactured in accordance with the claimed technical solution are characterized with the following properties (see Table, Example 1).
- Example 1 Composition of the alloy: niobium 0.94-0.97% (wt.), stannum 1.15-1.20% (wt.), iron 0.40-0.46% (wt.), chromium 0.004-0.005% (wt.), carbon 0.008-0.009% (wt.), oxygen 0.10-0.11% (wt.), silicon 0.0055-0.0060% (wt.).
- the initial alloying components are mixed with zirconium magnesiothermal sponge, and then consumable electrodes are formed and melted by three-stage vacuum arc remelting.
- tubular products ⁇ 12.60 ⁇ 10.90 mm manufactured in accordance with the claimed technical solution are characterized with the following properties (see Table, Example 2).
- Example 1 Composition of the alloy: niobium 0.90-0.93% (wt.), stannum 1.18-1.22% (wt.), iron 0.82-0.87% (wt.), chromium 0.008-0.009% (wt.), carbon 0.010-0.011% (wt.), oxygen 0.082-0.086% (wt.), silicon 0.0052-0.0058% (wt.).
- the initial alloying components are mixed with zirconium magnesiothermal sponge, and then consumable electrodes are formed and melted by two-stage vacuum arc remelting.
- tubular products ⁇ 13.00 ⁇ 11.00 mm manufactured in accordance with the claimed technical solution are characterized with the following properties (see Table, Example 3).
- the manufacturing technology for zirconium tubular products includes the following operations. Melting of the alloy ingot consisting of: niobium 1.06-1.09% (wt.), stannum 1.28-1.30% (wt.), iron 0.65-0.68% (wt.), chromium 0.009-0.011% (wt.), carbon 0.009-0.010% (wt.), oxygen 0.08-0.09% (wt.), silicon 0.009-0.010% (wt.).
- the initial alloying components are mixed with electrolytic zirconium powder, and then consumable electrodes are formed and melted by two-stage vacuum arc remelting.
- the side surface of the ingot is processed mechanically.
- the ingot is heated to the temperature of 980° C. Multi-stage hot forging of the ingot is carried out within the temperature range of 980 to 720° C. with intermediate heat-up within the temperature range of 890 to 850° C.
- the total deformation ⁇ ⁇ for multi-stage hot forging of the ingot is 93%. Heating and intermediate heat-up of the ingot is carried out in the electric resistance-type furnace.
- Round-profile blanks ⁇ 109 ⁇ 28.5 mm are manufactured by mechanical processing of the forged pieces.
- Heating of the billets for hot pressing is carried out in the electric resistance-type furnace.
- the produced billets are rolled at the cold reducing mills of HPT, HPTR type in 6 runs; in this case the tubular coefficient Q is within the range of 1.0-6.4.
- the set of the following final finishing operations is carried out: jet etching, alkali treatment, grinding of the surface.
- the thin-walled and thick-walled sections of the finished pipe have approximately the same cumulative deformation degree providing for uniform mechanical properties of the tubular products after the final vacuum thermal treatment.
- tubular products ⁇ 12.60 ⁇ 11.24 (10.1) mm manufactured in accordance with the claimed technical solution are characterized with the following properties (see Table, Example 4).
- Example 4 To be embodied in the same way as Example 4.
- tubular products ⁇ 12.60 ⁇ 10.90 (8.8) mm manufactured in accordance with the claimed technical solution are characterized with the following properties (see Table, Example 5).
- the presented manufacturing method for tubular products ensures high strength characteristics and corrosion resistance of the tubular products.
Abstract
Manufacturing method for tubular products made of zirconium-based alloy includes melting an ingot by multiple vacuum arc remelting, mechanical processing of the ingot, heating, multi-stage hot forging of the ingot for production of a forged piece, subsequent mechanical processing of the forged piece for production of the a round-profile blank, manufacturing of tubular billets, their quenching and tempering, application of a protective coating, heating to a hot pressing temperature, hot pressing, removal of the protective coating, vacuum thermal treatment, multiple cold rolling steps in order to produce tubular products, with intermediate vacuum thermal treatment after each cold rolling, and a final vacuum thermal treatment being carried out at a final size with subsequent final finishing operations. The tubular products can be used as the structural components of a core in water-cooled nuclear reactors. The method can provide increased processibility, high strength, and corrosion resistance of tubular products.
Description
- The invention is referred to the nuclear technical field, particularly to production of zirconium alloy tubular products used as the structural components of the core in water-cooled nuclear reactors, including the reactors of VVER and PWR type.
- Zirconium alloys are used as the materials for structural components of power nuclear reactors due to their unique properties: small thermal absorption section as well as physical and mechanical properties. The requirements for corrosion resistance and hydrogen absorption in high-temperature water and water steam, strength, irradiation growth, thermal and thermal-radiation creep are imposed on the zirconium alloy products for the reactor core. The materials shall also have high processibility characteristics. Properties and processibility of the products made of this alloy depend not only on the composition but also on their manufacturing method including the ingot melting, hot and cold processing, thermal treatment regimes for the intermediate and final size, as well as the final finishing operations.
- The patent “Manufacturing Method for Zirconium Alloy Tubular Products (Variants)” (RU 2123065C1, published on 12 Mar. 1997, cl. C22F/1/18) including preliminary hot deformation of the melted ingot, production of the tubular billet by hot forming (extrusion), quenching, mechanical processing and tempering, cold deformation with intermediate thermal treatment and final annealing for multi-component zirconium alloy is known.
- The drawbacks of this method reside in the fact that no protective coating is applied on the billets prior to hot extrusion resulting in oxidation of the metal in the course of the process and reduction of the processibility of tubular products, and no final finishing operations enabling to remove residual process contaminations from the surface of tubular products and reduce the surface roughness are provided thus decreasing corrosion resistance of the products.
- The patent “Manufacturing Method for Zirconium Alloy Products” RU 2110600C1 (published on 10 May 1998, cl. C22F/1/18) including manufacturing of the primary blank from the ingot by hot forming (extrusion), subsequent hot forming of the intermediate billet, quenching and tempering of the cut-to-length sections, hot forming, tempering and cold rolling is known.
- The drawbacks of this method reside in the fact that no protective coating is applied prior to hot extrusion resulting in oxidation of the metal in the course of the process and reduction of the processibility of tubular products, and no final finishing operations enabling to remove residual process contaminations from the surface of tubular products and reduce the surface roughness are provided thus decreasing corrosion resistance of the products.
- The patent “Tubes Made of Zirconium-Based Alloys and Their Manufacturing Method” RU 2298042C2 (published on 27 Apr. 2004, cl. C22F/1/18C21D1/18, C22C16/00) is known. The manufacturing method includes homogenizing processing of the extruded hollow billets, their quenching with water, stress relieving, double-stage cold rolling with intermediate and final annealing.
- The drawbacks of this patent reside in the fact that no protective coating is applied prior to hot extrusion resulting in oxidation of the metal in the course of the process and reduction of the processibility of tubular products. Application of the double-rolling cold processing scheme with final homogenizing processing in the (α+β)-area enables to achieve high strength of the product, in this case annealing in the (α+β)-area results in generation of the metastable β-Zr-phase in the product structure affecting corrosion of zirconium alloys. The process flow diagram does not provide for any final finishing operations enabling to remove residual process contaminations from the surface of tubular products and reduce the surface roughness thus decreasing corrosion resistance of the products.
- The patent “Zirconium Alloy with Excellent Corrosion Resistance for Fuel Element Claddings and Their Manufacturing Method” US 2016/0307651A1 (published on 20 Oct. 2016, cl. G21C 3/07, B22D 21/00, B22D 7/00, C22C 16/00, C22F 1/18) is the closest to the claimed method. The patent specifies the composition of corrosion-resistant zirconium alloy and the method for manufacturing of fuel element claddings made of this alloy, including the ingot melting, the ingot coating with the protective steel shell, thermal treatment of the ingot together with the shell prior to hot rolling, hot rolling, removal of the protective steel coating, thermal treatment of hot-rolled tubular billets, three runs of cold rolling, intermediate thermal treatment after each rolling and final thermal treatment.
- Drawbacks of the method: application of the carbon-containing steel shell which can interact with zirconium alloy at the hot rolling temperature with generation of carbides. Hot rolling of the ingot does not provide for uniform processing of the cast structure and is characterized by axial porosity of the billets. The number and size of the pores increase from the periphery towards the centers of billets thus resulting in deterioration of the material processibility. Low temperatures of intermediate annealing (570-590° C. for the 1st run, 560-580° C. for the 2nd run, 560-580° C. for the 3rd run) for the selected deformation manufacturing scheme (30-40% of deformation at the first and the third stages, and 50-60%—at the second stage of cold deformation) are insufficient for relaxation of residual stresses and completion of recrystallization processes that affects the material processibility and its resistance to creep and irradiation growth. Use of the three-level long-term final annealing (1st level—460-470° C., 2nd level—510-520° C., 3rd level—580-590° C.) enables to achieve the increased material strength level; in this case the characteristics of creep and irradiation growth resistance are also deteriorated primarily due to incomplete recrystallization process. Besides, use of hot rolling at T=630-650° C. in combination with few stages of cold deformation and low annealing temperatures prevents from completion of the metastable β-Zr-phase breakage and fission process resulting in deterioration of the product corrosion resistance. The process flow diagram does not provide for any final finishing operations enabling to remove residual process contaminations from the surface of tubular products and reduce the surface roughness thus decreasing corrosion resistance of the products.
- The purpose of this invention is to develop the manufacturing method for the tubular products used as the structural components of the core in water-cooled nuclear reactors, including the reactors of VVER and PWR type.
- The technical result is processibility of the material at all stages of hot and cold pressure shaping applied in the course of tubular product manufacturing as well as high strength characteristics and corrosion resistance of the tubular products.
- The technical result is achieved in the manufacturing method for the tubular products made of zirconium-based alloy containing (% wt.): niobium—0.9-1.7; stannum—0.5-2.0; iron—0.3-1.0; chromium—0.002-0.200, carbon—0.003-0.040, oxygen—0.04-0.15, silicon—0.002-0.15, zirconium—all the rest, including the ingot melting by multiple vacuum arc remelting, mechanical processing of the ingot, heating, multi-stage hot forging of the ingot for production of the forged piece, subsequent mechanical processing of the forged piece for production of the round-profile blank, manufacturing of tubular billets, their quenching and tempering, application of the protective coating and heating to the hot pressing temperature, hot pressing, removal of the protective coating, vacuum thermal treatment, multiple cold rolling with the total deformation degree of 25.6-56.8% per a run and the tubular coefficient of Q=1.0-6.4 in order to produce tubular products, with intermediate vacuum thermal treatment after each cold rolling, and the final vacuum thermal treatment is carried out at the final size with subsequent final finishing operations.
- Multi-stage hot forging of the ingot is carried out at the temperature of 980° C. to 720° C. with the total deformation degree of up to 93% and with intermediate heating at the temperature of 890° C. to 850° C.
- Tubular billets are produced by drilling of the axial center hole and subsequent boring of the axial center hole in the round-profile blank divided into cut-to-length sections.
- Quenching is carried out at the temperature of 1050-1100° C. and tempering at the temperature of 450-600° C.
- Hot pressing of the tubular billet is carried out at the temperature of 640° C. to 600° C. and the elongation ratio of μ=8.5-9.0.
- Vacuum thermal treatment of the tubular billets in the intervals between hot pressing and cold rolling is carried out at the temperature of 605-630° C.
- Multiple cold rolling of the tubular billets is carried out with the total deformation degree of 41.8-56.8% per a run and the tubular coefficient of Q=1.0-1.6 for the tubular products of uniform cross-section.
- Multiple cold rolling of the tubular billets is carried out with the total deformation degree of 25.6-56.5% per a run and the tubular coefficient of Q=1.0-6.4 for the tubular products of variable cross-section.
- Vacuum thermal treatment of the tubular billets in the intervals between cold rollings is carried out at the temperature of 570-630° C.
- The final vacuum thermal treatment of the tubular products is carried out at the temperature of 535-545° C.
- The final vacuum thermal treatment of the tubular products is carried out at the temperature of 600-620° C.
- Vacuum thermal treatment of the tubular products is carried out at the residual pressure in the furnace not exceeding 1·10−4-1·10−5 mm Hg.
- Chemical and mechanical processing of the surfaces is carried out at the final size of the tubular products.
- The selected proportion of alloying components in the zirconium alloy provides for the processing properties, corrosion resistance, stable characteristics of mechanical properties and deformation resistance of the tubular products.
- The advantage of the tubular product manufacturing in accordance with the claimed method resides in the fact that hot thermo-mechanical treatment ensures uniform processing of the cast structure along the ingot length and cross-section, and application of the protective coating provides for protection against gas pickup and prevents diffusion interaction between the coating and the tubular billet. The process also provides for manufacturing of the tubular products with the maximum possible fracture viscosity and ductility level for this composition. Multiple cold rolling with the total deformation degree of 25.6-56.8% per a run and the tubular coefficient of Q=1.0-6.4 with intermediate vacuum thermal treatment results in formation of the material structure with the minimum residual stresses at the processing stages and development of recrystallization processes thus improving processibility of the tubular products. Depending on the necessary requirements for strength of the tubular products the final vacuum thermal treatment of the tubular products is carried out in two different temperature ranges. The first range (535-545° C.) provides for formation of the homogeneous partially recrystallized structure (the recrystallization degree of at least 40%), and the second range (600-620° C.) provides for formation of the homogeneous recrystallized structure (the recrystallization degree of 100%).
- Final finishing operations provide for the surface roughness Ra of less than 0.8 μm on the outer and inner surface thus increasing stability of the corrosion properties for the products.
- The method is embodied in the following way:
- In accordance with the claimed technical solution the manufacturing technology for zirconium tubular products includes the following operations. Melting of the alloy ingot consisting of: niobium 1.05-1.07% (wt.), stannum 1.24-1.27% (wt.), iron 0.31-0.34% (wt.), chromium 0.0025-0.003% (wt.), carbon 0.011-0.019% (wt.), oxygen 0.064-0.065% (wt.), silicon 0.0025-0.0035% (wt.), zirconium—all the rest. The initial alloying components are mixed with electrolytic zirconium powder, and then consumable electrodes are formed and melted by two-stage vacuum arc remelting. The side surface of the ingot is processed mechanically. The ingot is heated to the temperature of 980° C. Multi-stage hot forging of the ingot at the first stage is carried out at the temperature of 980° C., at the last stage—at the temperature of 720° C., with intermediate heating within the temperature range of 890° C. to 850° C.
- The total deformation Σε for hot forging of the ingot is 93%. Heating and intermediate heat-up of the ingot is carried out in the electric resistance-type furnace. Round-profile blanks Ø109×28.5 mm are manufactured by mechanical processing of the forged pieces.
- Tubular billets are produced by drilling of the axial center hole and subsequent boring of the axial center hole in the round-profile blank divided into cut-to-length sections.
- Quenching is carried out at the temperature of 1050-1100° C., and tempering—at the temperature of 450-600° C. The surface roughness of the billets is not more than Ra=2.5 μm. Then the coating is applied on the tubular billets in order to protect them against gas pickup in the course of subsequent heating and hot pressing processes (for example, copper through the use of the copper coating application operation).
- Heating of the tubular billets for hot pressing is carried out in the electric resistance-type furnace. The heating temperature of the tubular billets prior to pressing is within the range of 640° C. to 600° C. Pressing is carried out with the elongation ratio of μ=8.9. Then the copper coating is removed.
- Then the tubular billets are sent for vacuum thermal treatment at the temperature of T=605-630° C. The tubular billets are rolled on the cold reducing mills of HPT, HPTR, KPW type in 5 runs with the total deformation Σε of 41.8 to 56.5% per a run; in this case the tubular coefficient Q is within the range of 1.00-1.6, and the tubular products of uniform cross-section are produced. Intermediate vacuum thermal treatment is carried out within the temperature range of 570° C. to 610° C. The final vacuum thermal treatment is carried out at the temperature of T=535-545° C. or T=600-620° C. Vacuum furnaces with the underpressure level of at least 1·10−4-1·10−5 mm Hg are used.
- The tubes are subjected to a set of operations subsequent to the final annealing and trimming, particularly: jet etching, alkali treatment, grinding of the surface.
- The alloy tubular products Ø12.60×11.24 mm manufactured in accordance with the claimed technical solution are characterized with the following properties (see Table, Example 1).
- To be embodied in the same way as Example 1. Composition of the alloy: niobium 0.94-0.97% (wt.), stannum 1.15-1.20% (wt.), iron 0.40-0.46% (wt.), chromium 0.004-0.005% (wt.), carbon 0.008-0.009% (wt.), oxygen 0.10-0.11% (wt.), silicon 0.0055-0.0060% (wt.). The initial alloying components are mixed with zirconium magnesiothermal sponge, and then consumable electrodes are formed and melted by three-stage vacuum arc remelting.
- The tubular products Ø12.60×10.90 mm manufactured in accordance with the claimed technical solution are characterized with the following properties (see Table, Example 2).
- To be embodied in the same way as Example 1. Composition of the alloy: niobium 0.90-0.93% (wt.), stannum 1.18-1.22% (wt.), iron 0.82-0.87% (wt.), chromium 0.008-0.009% (wt.), carbon 0.010-0.011% (wt.), oxygen 0.082-0.086% (wt.), silicon 0.0052-0.0058% (wt.). The initial alloying components are mixed with zirconium magnesiothermal sponge, and then consumable electrodes are formed and melted by two-stage vacuum arc remelting.
- The tubular products Ø13.00×11.00 mm manufactured in accordance with the claimed technical solution are characterized with the following properties (see Table, Example 3).
- In accordance with the claimed technical solution the manufacturing technology for zirconium tubular products includes the following operations. Melting of the alloy ingot consisting of: niobium 1.06-1.09% (wt.), stannum 1.28-1.30% (wt.), iron 0.65-0.68% (wt.), chromium 0.009-0.011% (wt.), carbon 0.009-0.010% (wt.), oxygen 0.08-0.09% (wt.), silicon 0.009-0.010% (wt.). The initial alloying components are mixed with electrolytic zirconium powder, and then consumable electrodes are formed and melted by two-stage vacuum arc remelting. The side surface of the ingot is processed mechanically. The ingot is heated to the temperature of 980° C. Multi-stage hot forging of the ingot is carried out within the temperature range of 980 to 720° C. with intermediate heat-up within the temperature range of 890 to 850° C.
- The total deformation Σε for multi-stage hot forging of the ingot is 93%. Heating and intermediate heat-up of the ingot is carried out in the electric resistance-type furnace. Round-profile blanks Ø109×28.5 mm are manufactured by mechanical processing of the forged pieces. Tubular billets are produced by drilling of the axial center hole and subsequent boring of the axial center hole in the round-profile blank divided into cut-to-length sections. The surface roughness of the billets is not more than Ra=2.5 μm. Quenching is carried out at the temperature of 1050-1100° C. and tempering at the temperature of 450-600° C.
- Then copper coating is applied on the billets in order to protect them against gas pickup in the course of subsequent heating and hot pressing processes.
- Heating of the billets for hot pressing is carried out in the electric resistance-type furnace. The heating temperature of the billet prior to pressing is within the range of T=640-600° C. Pressing is carried out with the elongation ratio of μ=8.9. Then the copper coating is removed.
- Subsequently the billets are sent for vacuum thermal treatment at the temperature of T=605-630° C. Then the produced billets are rolled at the cold reducing mills of HPT, HPTR type in 6 runs; in this case the tubular coefficient Q is within the range of 1.0-6.4. The variable cross-section of tubular billets is formed through the use of the combined multi-diameter expander with the total deformation degree of Σε=25.6-56.5%.
- Intermediate vacuum thermal treatment is carried out within the temperature range of T=575-590° C. The final vacuum treatment of the tubular products is carried out at the temperature of T=535° C. or T=610° C. depending on the strength requirements. Vacuum furnaces with the underpressure level of at least 1·10−4-1·10−5 mm Hg are used.
- Subsequent to the final vacuum thermal treatment of the tubular products the set of the following final finishing operations is carried out: jet etching, alkali treatment, grinding of the surface.
- Subsequent to formation of the tubular products of variable cross-section from the tubular billet of variable cross-section with different cumulative deformation degree in various sections of the tubular billet the thin-walled and thick-walled sections of the finished pipe have approximately the same cumulative deformation degree providing for uniform mechanical properties of the tubular products after the final vacuum thermal treatment.
- The tubular products Ø12.60×11.24 (10.1) mm manufactured in accordance with the claimed technical solution are characterized with the following properties (see Table, Example 4).
- To be embodied in the same way as Example 4.
- The tubular products Ø12.60×10.90 (8.8) mm manufactured in accordance with the claimed technical solution are characterized with the following properties (see Table, Example 5).
- Therefore, the presented manufacturing method for tubular products ensures high strength characteristics and corrosion resistance of the tubular products.
-
TABLE Properties of the tubes manufactured of the Zr—Nb—Sn—Fe system alloy in accordance with the claimed technical solution Number of Chemical remeltings/weight Mechanical properties composition of the final Tube σb ⊥, σ0.2 ⊥ δ⊥, σ0.2 //, Example of the alloy, remelting dimensions, MPa MPa % σb //,MPa MPa No. % (wt.) ingot, tons mm Ttest = 20° C. 1 2 3 4 5 6 7 8 9 1 Nb 2 vacuum arc Ø12.60 × 11.24 52.5 46.0 24.6 56.3 43.3 1.05-1.07, remeltings/3.5 FVTT* Sn temperature 1.24-1.27, 540° C., Fe 3 hours 0.31-0.34, Ø12.60 × 11.24 51 36 38 52 35 Cr FVTT* 0.0025-0.003, temperature C 610° C., 0.011-0.019, 3 hours O 0.064-0.065, Si 0.0025-0.0035, Zr- all the rest 2 Nb 3 vacuum arc Ø12.60 × 10.90 55.5 49 22.5 56.5 41.5 0.94-0.97, remeltings/3.5 FVTT* Sn temperature 1.15-1.20, 540° C., Fe 3 hours 0.40-0.46, Cr 0.004-0.005, C 0.008-0.009, O 0.10-0.11, Si 0.0055-0.0060, Zr- all the rest 3 Nb 2 vacuum arc Ø13.00 × 11.00 55.5 48 19 57 44 0.9-0.93, remeltings/1.8 FVTT* Sn temperature 1.18-1.22, 545° C., Fe 3 hours 0.82-0.87, Cr 0.008-0.009, C 0.01-0.011, O 0.082-0.086, Si 0.0052-0.0058, Zr- all the rest 4 Nb 2 vacuum arc Ø12.60 × 11.24 53 47.5 24 55 41.5 1.06-1.09% (wt.), remeltings/3.5 (10.1) FVTT* Sn temperature 1.28-1.30% (wt.), 535° C., 3 Fe hours 0.65-0.68% (wt.), Cr 0.009-0.011% (wt.), C 0.009-0.010% (wt.), O 0.08-0.09% (wt.), Si 0.009-0.010% (wt.), Zr- all the rest 5 Nb 2 vacuum arc Ø12.60 × 10.90 52.5 45.5 32 54.1 40.5 1.06-1.09, remeltings/3.5 (8.8) FVTT* Sn temperature 1.28-1.30, 600° C., Fe 3 hours 0.65-0.68, Cr 0.009-0.011, C 0.009-0.010, O 0.08-0.090, Si 0.009-0.01, Zr- all the rest Corrosion 400° C. Mechanical properties τ = 3600 h δ//, σb ⊥, σ0.2 ⊥, δ⊥, σb //, σ0.2 //, δ//, Weight Example % MPa MPa % MPa MPa % gain, Roughness No. Ttest = 20° C. Ttest = 350° C. mg/dm2 Ra, μm 1 10 11 12 13 14 15 16 17 18 1 39.1 28.1 27.0 24.6 31.4 22.2 48.2 149-156 Outer surf. <0.5 Inner surf. <0.8 36 28 15.2 45 29 16 35 150-160 Outer surf. <0.5 Inner surf. <0.8 2 33 30 27 27 31.5 20 40.5 148-152 Outer surf. <0.5 Inner surf. <0.8 3 31.5 30 27.5 24.5 34 21.5 37-39 150-154 Outer surf. <0.5 Inner surf. <0.8 4 35.5 29.5 26.5 27.5 33 24 37.5 147-154 Outer surf. <0.5 Inner surf. <0.8 5 36 27 26 31 30.5 22 36 152-160 Outer surf. <0.5 Inner surf. <0.8 FVTT*—Final Vacuum Thermal Treatment
Claims (13)
1. Manufacturing method for tubular products made of zirconium-based alloy containing (% wt.): niobium—0.9-1.7; stannum—0.5-2.0; iron—0.3-1.0; chromium—0.002-0.200, carbon—0.003-0.040, oxygen—0.04-0.15, silicon—0.002-0.15, zirconium—all the rest, including the ingot melting by multiple vacuum arc remelting, mechanical processing of the ingot, heating, multi-stage hot forging of the ingot for production of the forged piece, subsequent mechanical processing of the forged piece for production of the round-profile blank, manufacturing of tubular billets, their quenching and tempering, application of the protective coating and heating to the hot pressing temperature, hot pressing, removal of the protective coating, vacuum thermal treatment, multiple cold rolling with the total deformation degree of 25.6-56.8% per a run and the tubular coefficient of Q=1.0-6.4 in order to produce tubular products, with intermediate vacuum thermal treatment after each cold rolling, and the final vacuum thermal treatment is carried out at the final size with subsequent final finishing operations.
2. The method as claimed in claim 1 characterized in that multi-stage hot forging of the ingot is carried out at the temperature of 980° C. to 720° C. with the total deformation degree of 93% and with intermediate heat-up at the temperature of 890° C. to 850° C.
3. The method as claimed in claim 1 characterized in that tubular billets are produced by drilling of the axial center hole and subsequent boring of the axial center hole in the round-profile blank divided into cut-to-length sections.
4. The method as claimed in claim 1 characterized in that quenching is carried out at the temperature of 1050-1100° C. and tempering—at the temperature of 450-600° C.
5. The method as claimed in claim 1 characterized in that hot pressing of the tubular billet is carried out at the temperature of 640° C. to 600° C. and with the elongation ratio of μ=8.5-9.0.
6. The method as claimed in claim 1 characterized in that vacuum thermal treatment of the tubular billets in the intervals between hot pressing and cold rolling is carried out at the temperature of 605-630° C.
7. The method as claimed in claim 1 characterized in that multiple cold rolling of the tubular billets is carried out with the total deformation degree of 41.8-56.8% per a run and the tubular coefficient of Q=1.0-1.6 for the tubular products of uniform cross-section.
8. The method as claimed in claim 1 characterized in that multiple cold rolling of the tubular billets is carried out with the total deformation degree of 25.6-56.5% per a run and the tubular coefficient of Q=1.0-6.4 for the tubular products of variable cross-section.
9. The method as claimed in claim 1 characterized in that vacuum thermal treatment of the tubular billets in the intervals between cold rollings is carried out at the temperature of 570-630° C.
10. The method as claimed in claim 1 characterized in that the final vacuum thermal treatment of the tubular products is carried out at the temperature of 535-545° C.
11. The method as claimed in claim 1 characterized in that the final vacuum thermal treatment of the tubular products is carried out at the temperature of 600-620° C.
12. The method as claimed in claim 6 , characterized in that vacuum thermal treatment of the tubular products is carried out at a residual pressure in the furnace not exceeding 1·10−4-1·10−5 mm Hg.
13. The method as claimed in claim 1 characterized in that chemical and mechanical treatment of the surfaces is carried out at the final size of the tubular products.
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PCT/RU2019/001024 WO2021133195A1 (en) | 2019-12-26 | 2019-12-26 | Method of producing tubular products from a zirconium-based alloy |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3690850A (en) * | 1966-02-01 | 1972-09-12 | Sandvikens Jernverks Ab | Zirconium alloy tube with zirconium hydride inclusions |
US5560790A (en) * | 1993-03-04 | 1996-10-01 | A.A. Bochvar All-Russian Inorganic Materials Research Institute | Zirconium-based material, products made from said material for use in the nuclear reactor core, and process for producing such products |
US20120079864A1 (en) * | 2010-09-30 | 2012-04-05 | Sun Doo Kim | Pilger die and pilger mandrel for manufacturing dashpot tube for nuclear fuel assembly, method of manufacturing the pilger die and the pilger mandrel, and dashpot tube for nuclear fuel assembly |
US20160307651A1 (en) * | 2015-04-14 | 2016-10-20 | Kepco Nuclear Fuel Co., Ltd. | Zirconium alloy having excellent corrosion resistance for nuclear fuel cladding tube and method of manufacturing the same |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
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EP0071193B1 (en) * | 1981-07-29 | 1988-06-01 | Hitachi, Ltd. | Process for producing zirconium-based alloy |
RU2110600C1 (en) | 1996-09-10 | 1998-05-10 | Открытое акционерное общество "Чепецкий механический завод" | Method for producing articles from zirconium alloys |
UA53696C2 (en) | 1997-03-12 | 2003-02-17 | Откритоє Акціонєрноє Общєство "Чєпєцкій Мєханічєскій Завод" | A method for producing tubing products from zirconium alloys (variants) |
RU2298042C2 (en) | 2004-12-24 | 2007-04-27 | Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт неорганических материалов им. акад. А.А. Бочвара" | Tubes of zirconium-based alloys and a method for manufacture thereof |
-
2019
- 2019-12-26 KR KR1020217038914A patent/KR20220023762A/en not_active Application Discontinuation
- 2019-12-26 WO PCT/RU2019/001024 patent/WO2021133195A1/en active Application Filing
- 2019-12-26 CN CN201980044246.XA patent/CN113316490A/en active Pending
- 2019-12-26 EP EP19932280.1A patent/EP4082686A4/en active Pending
- 2019-12-26 US US17/257,283 patent/US20220316041A1/en active Pending
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2020
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3690850A (en) * | 1966-02-01 | 1972-09-12 | Sandvikens Jernverks Ab | Zirconium alloy tube with zirconium hydride inclusions |
US5560790A (en) * | 1993-03-04 | 1996-10-01 | A.A. Bochvar All-Russian Inorganic Materials Research Institute | Zirconium-based material, products made from said material for use in the nuclear reactor core, and process for producing such products |
US20120079864A1 (en) * | 2010-09-30 | 2012-04-05 | Sun Doo Kim | Pilger die and pilger mandrel for manufacturing dashpot tube for nuclear fuel assembly, method of manufacturing the pilger die and the pilger mandrel, and dashpot tube for nuclear fuel assembly |
US20160307651A1 (en) * | 2015-04-14 | 2016-10-20 | Kepco Nuclear Fuel Co., Ltd. | Zirconium alloy having excellent corrosion resistance for nuclear fuel cladding tube and method of manufacturing the same |
Non-Patent Citations (1)
Title |
---|
Machine translation of Zhang Ruiqian et. al. [CN105441716A] (Year: 2016) * |
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WO2021133195A1 (en) | 2021-07-01 |
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ZA202008085B (en) | 2022-07-27 |
KR20220023762A (en) | 2022-03-02 |
CN113316490A (en) | 2021-08-27 |
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